Lubricating composition



I Patented July 2, 1946 LUBRICATING COMPOSITION Rush F. McCleary, Beacon, N. Y., assignor to The Texas Company, New York, N. Y., a corporation of Delaware No Drawing. Application March 2c, 1943,

, sem No. 480,680

14 Claims.

The present invention relates to improved lubricants and particularly to alubricating composition containing one or more additive ingredients capable of imparting detergent and anticorrosive properties thereto.

The additive ingredients of the present invention are prepared from the phenolic compositions present inor derived from the oils extracted from the Anacardium genus of the Anacardiaceae family. The oils included within this classification are the oils and liquids commonly referred to as cashew nut shell oil, marking nut shell oil, Japanese lac, etc., whose chemical composition depends upon the particular method of extraction used. It is the consensus of the authorities on these extracted oils and liquids that the chemical composition of the naturally-occurring oils consists primarily of various types of aro- (CzoHaoOz) etc. These aromatic derivatives, and the other aromatic derivatives which may be present in Or derived from the oils which have not been isolated, are very unstable-and in the presence of heat form decomposition products or oil-insoluble polymerization products.

I For the purposes of this invention, one of these naturally-occurring oils, namely, cashew nut shell oil, will be used .as illustrating the types of derivatives' and reactions representative of the components of the oils' falling within this natural classificatiom- Cashew. nut shell oil, when obtained by solvent extraction, consists primarily of 90% anacardic acid and 10% cardol. .The anacardic acid portion of this solvent-extracted oil, which is described as a salicylic acid homolog, decomposes at slightly elevated temperatures with the evolution of carbon dioxide to yield cardanol, which is 'a phenol containing an unsaturated alkyl radical (C14H27) in the meta position. This decomposition is particularly noticed in the cashew nut shell oil obtained by a thermal extraction process which contains varying amounts of anacardic acid, usually around 16%, with the balance made up of a major proportion of cardanol and a minor proportion of cardol.

It has been-foundthat certain derivatives of these phenolic-compositions present in or derivedfrom the oils extracted from the Anacardlum genus of the Anacardiaceae family, when incorporated in a lubricating composition, impart enhanced detergent properties thereto. The de fication includes all those aromatic derivatives obtained from these oils which possess at least one hydroxyl group attached to the aromatic nu- I cleus irrespectiveof the presence of other oxygenmatic derivatives, such as anacardic acid (0221-1320:), cardol (U3235204), cardanol (C20H32O), anacardol '(CmHsuO), urushiol the oils extracted from the Anacardium genus oi.

containing radicals, which may also be attached to the nucleus together with mixtures thereof.

The aliphatic-ether-alcohol derivatives of these phenolic compositions are those in which a hydroxyl or sulfhydryl radical is displaced from the aromatic nucleus of'the phenolic composition by means of an aliphatic radical linked to the aromatic ,nucleus through an ether linkage at the position of one or more of the original hydroxyl groups. The displaced hydroxyl or sulfhydryl radical may remain as such. in the final product or the replaceable hydrogen thereof may be replaced by a metal to form the metal alcoholate derivative, depending upon the type of improving qualities desired inthe compounded lubricant.

The additive ingredients of the present invention may be described as those oil-miscible derivatives of the phenolic compositions present'in in which A is a phenoxy radical derived from the phenolic compositions present in or derived from the Anacardiaceae family, R is an aliphatic radical, X may be either oxygen or sulfur, Y may be either hydrogen or a metal, and a and n are integers of one or more. The value of It may be varied in accordance with the number of hydroxyl radicals present on the nucleus of the phenolic composition. The value of a is preferably within the range of from 1 to 10. The radical R, although referring broadly to any aliphatic radical, is preferably one containing from 1 to 10 carbon atoms which may contain such substituents as halogen, amino, nitro, sulfur, etc., radicals attached thereto. The symbol Y designates which metal has one valence thereof attached to the constituent X of the formula. The metals contemplated within the designation of Y may rivatives of these phenolic compositions with which the present invention is concerned are the oil-miscible aliphatic-ether-alcohol and the aliphatic-ether-alcoholate derivatives of these phenolic compositions. V

In referring to the phenolic compositions present in or derived from the oils extracted from,

be any of the following metals, such as lithium, sodium, potassium, calcium, barium, strontium,

magnesimn, zinc, iron cadmium, nickel, manthe Anacardium oils which are extremely unstable and susceptible to polymerization and condensation reactions, it may be preferable to first stabilize these compositions before proceeding in the preparation of the derivatives of the present iii-- vention. Such stabilizing processes include partial hydrogenation or addition reactions which render the unsaturated alkyl constituents of these compositions less reactive and may, in effect, enhance the improving properties of the final prodnot as an addition agent. It is therefore to be understood that the scope of the invention includes the stabilized as well as the unstabilized phenolic compositions when reference is made. to these phenolic compositions or the phenoxy radical A.

Another factor to be considered in the interpretation of the scope of the invention is that when reference is made to the aliphatic-etheraloohol and alcoholate derivatives, such nomenclature is intended to include the derivatives in which the alcohol or alcoholate portion thereof is replaced by a sulfhydryl radical or the metal salts of such compounds. 7

These additive components may be incorporated in a hydrocarbon oil, and preferably in a mineral lubricating oil, in amounts varying between 0.01 and 5.0% by weight, depending upon the type of base oil and the degree of improvement desired. It has been found that when using a mineral lubricating oil as the base oil in a lubricating composition designed for service in internal combustion engines the range of proportions between 0.1 and 2.0% by weight is particularly eflective.

In preparing the additive components of the" present invention any of the classical methods of synthesis may be used. The particular method chosen depends upon the conditions of reaction and the stability of the phenolic composition. It is preferable to select a method of preparation which is carried out at low temperatures and which either does not yield acidic by-products or in which the acidic by-products are removed from the reaction zone. These conditions of reaction, however, may be modified if the starting material has been stabilized by partial hydrogenation or addition reactions, such as a halogenation or sulfurization reaction.

For purposes of illustration a few of the generally-accepted methods of synthesis which may be used in the preparation of these derivatives will be. presented by means of empirical reactions. In these reactions the symbol AH will be used to designate the phenolic composition obtained from the Anacardium oils in which A is the phenoxy radical previously described.

1 AH Cl-CHr-CHz-OH NaOH A-CHz-OHs-OH (2) m olmo NaOH A-CHr-CHz-OH a) in oaeno NaOH A-(OHz-CHz-Oh H on. cm 4 Am o -onl-t-on. A-om-t-cm (6) ANa Cl-(CHahu-Cl A-(CHrhr-Cl form a 50% concentrate.

formula ARiOH is used to designate the aliphaticether-alcohol derivatives previously described:

inert ARiO Na (1) AR|OH Na solvent (toluene) liq. (2) 2AR OH Ca ---v (AR O):Ca

(3) 3AR OH AKOClHt): (AR OhAl (4) 2AR1OH Ba(OH)z (AlhOhBa The following specific examples illustrate the foregoing methods of preparing the compounds of the present invention:

Example I 46 grams of sodium were dissolved in two liters of liquid'ammonia. To this solution was then added a toluene solution of 510 grams of cardanol of cardanoxyethanol.

Example II The cardanoxyethanol, prepared in accordance with Example I, was then taken up b on liter of toluene and added to a solution of 45 grams of calcium in two liters of liquid ammonia. An additional liter of toluene was added and the ammonia allowed to evaporate. The toluene solution was then warmed and filtered. After filtering the solvent was removed by heating in vacuo and the residual calcium cardanoxyethylate was dissolved in an equal weight of 300 pal oil to The 50% concentrate analyzed as follows:

Per cent Ash 5.8 Calcium 3.2 Sodium 0.55

Example III 610 grams of cardanol (bromine No. 124; neut. No. 1.28; hydroxyl No. 188; per cent sulfur 0.02) were dissolved in 500 cos. of formula 30 alcohol and 120 grams of sodiurn hydroxide and 500 cos. of water were added. The reaction mixture was heated at IS- C. with vigorous stirring to insure complete solution of the sodium hydroxide. Thereafter 260 grams of ethylene chlorhydrin were added dropwise to the mixture over a period of one hour. The agitation was continued at 75-80 C. for two hours. Some toluene was added and the oil-layer washed three times in water. 850 grams of an S. A. E.-10 grade lubricating oil and 236 grams of anhydrous barium hydroxide were added to the washed cardanoxyethanol and the mixture heated under a reflux condenser equipped with an automatic separator until all the water and toluene were removed. The maximum reaction temperature was 225 C. The resulting product was filtered while still hot. The resulting 50% concentrate of barium cardanoxyethanol in a lubricating oil analyzed 8.88% harium.

, An additional feature of the present invention Reference is the combination of the foregoing additive component with an additive ingredient. possessing anti-corrosive properties when used in lubricatingcompositions designed for service in which bearing corrosion is an important factor. Thus, the combination of an aliphatic-ether-alcohol.or

- posed and utilized bythe prior art. It is prefer-' 2,4oaeeo A further test designed to indicate the efiectiveness of compounded oils under actual operating conditions was conducted. This test is a modification of the test described in Diese1Lubricant Test Manual, Laboratory Test No. 1,-issued by the Caterpillar Tractor Company. This testwas carried out in a single cylinder Diesel enable, however, to use an oil-soluble corrosion inhibitor which contains sulfur in the molecule in one form or another. Among the sulfur-containing anti-corrosive agents which are particularly adapted to the present invention may be mentioned the N-aliphatic thiocarbamates and the sulfur-containing kerosene fractions such as sive properties which may be added in combinationlwith the detergent components previously described, are usually within the proportionate range of 0.1 to 5% and preferably between the range of 0.2 to 3%, depending upon the degree of anti-corrosive properties desired.

To illustrate the effectiveness of the compounds of the present invention, together with combinations thereof with additive ingredients possessing anti-corrosive properties, the followe ing test results are presented. A corrosion test designed to predict the corrosion inhibiting properties of compounded oils with respect to the corrosion of copper-lead bearings was used. This test consists of a copper-lead bearing specimen encased in a special non-wear bushing. rotatably mounted on a stainless steel shaft and immersed in a glass pot of the oil to be tested; The tested oil was heated to a controlled temperature of 350 F. and continuously circulated between the bearing specimen and the shaft for ten hours.

Throughout the test the oil was continuously agitilted by means of copper baflles which acted as omdation accelerators. The bearing, specimen was weighed before the test and after the tenhour period and the loss in weight recorded in milligrams. The reference oil of this test was a mixed base solvent-refined, dewaxed, Mid-Continent lubricating oil of an S. A. E. 30 grade.

To the reference oil was-added varying proporon tested 350 F- 011 260,300 Reference oil+0.75% calcium cardanoryethylate 291, 165 Reference oil-+9.75% calcium cardanoxyethylate+1.0%

sulfur-cont kerosene fraction Reference oil+l.0 barium cardanoryethylaten- Reference oil+l.0% barium cardanoxyethylate+0.5%

zinc dibutyl dithiocarbamate+0.26 suliur-containing kerosene ircctlon 'gine operating at 900 R. P. M. with a water jacket hours and fresh oil'added thereto. At the end of I each test period the engine was thoroughly examined and any carbonaceous deposits, lacquer and sludge formation, etc., were noted and the rincipal engine parts classified according to their condition. In the present instance the reference oil was a mixed base solvent-refined, dewaxed Mid-Continent lubricating oil of an S. A. E. 30 grade. The results of the test runs on the reference oil and-the reference oil containing 0.5%

calcium cardanoxyethylate are as'followsz Reference oil +0.15% Engine part Reference oil, hours cardanoxyethylate,

. 120 hours Heat grooves. Up to 50% plugged Up to 50% plugged. Ring grooves. Clean to heavy lacquer. Slight carbon in No. 1

and N o. 2 grooves. P1st0n skirt... Heavy varnish to lac- Trace varnish to light quer. varnish. Under piston Trace deposit Trace deposit. deposit. F1lter .i Clean to mesh pattern Clean tomesh pattern visi e. visible. Ring land Heavy varnish to car- Clean to heavy varnish.

hon deposit. Rlngs stuck... None None. Y Ring cleanli- Nos. 1, 2,3 clean, Nos. Nos. 1 and 2 clean, Nos. ness. 4, 5, 6 light lacquer. 3 and 6 trace lacquer, Nos. 4 and 5 light to medium lacquer.

Obviously many. modifications and variations of the invention, as hereinbefore set forth, may be made without departing from the spirit and scope thereof, and therefore only such limitations should be imposed as are indicated in the appended claims.

I claim:

1. A lubricating composition comprising a. ma- I 'Anacardium genus of the Anacardiaceae family.

3. A lubricating composition comprising a major amount of a hydrocarbon oil and 0.01-5% by weight or an oil-miscible aliphatic-ethebmetal alcoholate derivative of the phenolic compositions present in or derived from the oils extracted from v the Anacardium genus of the Anacardiaceae family.

4. A lubricating composition comprising a ma-- :lor amount of a hydrocarbon oil and 0.01-5% by weight of an oil-miscible aliphatic-ether-alkaline earth metal alcoholate derivativeof the phenolic compositions present in or derived from the oils tive ingredient possessing anti-corrosive properties.

6. A lubricating composition comprising a maior amount of a mineral lubricating oil and the combination of 0.01-5.0% by weight of an oilmisoible aliphatic-ether-metal alcoholate derivative oi. the phenolic compositions present in or derived from the oils extracted from the Anacardium genus of the Anacardiaceae family, and 0.1-5.0% by weight an oil-miscible sulfurcontaining additive ingredient possessing anticorrosive properties.

7. A lubricating composition comprising a mai'or amount of a mineral lubricating oil and the combination oi. (ml-5.0% by weight of an oilmiscible aliphatic-ether-metal alcoholate derivative of the phenolic compositions present in or.

derived from the oils extracted from the Anacardium genus of the Anacardiaceae family, and 0.1-5.0% by weight of an oil-miscible N-aliphatic di-thio-carbamate.

8. A lubricating composition comprising a ma- Jor amount of a hydrocarbon oil and o.o1-5.o%

by weight of an oil-miscible-compound of the,

general formula A( (RX) aY) a in which A is a phenoxy radical derived from the phenolic compositions present in or derived from the oils extracted hour the Anacardium genus or the Anacardiaceae family, R is an all phatic radical, X is a member'irom the group consisting of oxygen or sulfur, Y is a. member from the group consisting 01 hydrogen and a metal, and o and n are integers of at least one.

9. A lubricating composition comprising a ma- .ior amount-oi a mineral lubricating oil and 8 0.01%-5.0%-by weight of'an oil-miscible compound of the general formula consisting of oxygen or sulfur, Y is a member .from the group consisting of hydrogen and a metal, and a. and n are integers of at least one.

10. A lubricating composition comprising a major amount of a hydrocarbon oil and 0.01%- 5.0% by .weight of an oil-miscible compound of the general formula A( (RX) aY) n in which A is a phenoxy radical derived from the phenolic compositions present in or derived from the oils extracted from the Anacardium genus of the Anacardiaceae family, It is an aliphatic I radical, X is a member from the group con'sisting of oxygen or sulfur, Y is an alkaline earth metal, and a and .n are integers of at least one.

11. A lubricating composition comprising a major amount of a hydrocarbon oil and 0.01%- 5.0% by weight of an oil-miscible aliphatic-etheralcohol derivative of the phenolic compositions present in or derived from cashew nut shell oil.

12. A lubricating composition comprising a major amount of a hydrocarbon oil and 0.01- 5.0% by weight of an oil-miscible aliphatic-ethermet'al alcoholate derivative of the phenolic compositions present in or derived from cashew nut shell oil.

13. A lubricating composition comprising a maior amount or a hydrocarbon oil and cor-5.0% by weight of an oil-miscible aliphatic-ether-alkaline earth metal alcoholate derivative of the 7 phenolic compositions present in or derived from 

